Polymer swelling. XXV. Structure‐affinity correlation studies that involve poly(styrene‐co‐divinylbenzene) exposed to acetylenic liquids

The adsorption parameters (α) established for the monosubstituted acetylenic liquids in this investigation are consistent with expectation based on analogies with the log α_f = log α_i ‐ D_s(N_f ? N_i) relationships reported earlier for the many homologous series of liquids ZR, in which Z is a functional group having strong affinity for the pendent phenyl group of polystyrene and R is an alkyl substituent that is varied systematically. The order of relative Z‐affinities, based on α for the respective ZCH₂CH₃ molecules, confirm that the nature of Z is the major factor that affects α and that electronic and steric contributions from R are modifying effects, which are reflected in D_s. Comparisons of the results observed for HC?C(CH₂)_nZ′ liquids with those for HC?C(CH₂)_nH and with analogous pairs of Z(CH₂)_nZ′ series confirm that Z′ at the other end of the polymethylene chain can have a moderate positive effect or a marked negative effect on α, depending on whether the mode of adsorption to pendent phenyl groups is mono‐ or bidentate. This study also confirms that a sharp reversal in the roles played by the molecules participating in the adsorption process occurs when all of the hydrogen atoms covalently bonded to the center of unsaturation are replaced by alkyl substituents. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2611–2633, 1999